TWI438264B - Plastic film and infusion bag having oxigen absorption capability - Google Patents

Description

Plastic film with oxygen absorption function and infusion bag

The present invention relates to a plastic film for a medical container having an oxygen absorbing function, and an infusion bag using the plastic film.

The present invention is based on Japanese Patent Application No. 2009-251627, filed on Jan.

In addition to conventional glass bottles, medical containers such as infusions, liquid medicine bags, and enteral nutrients are currently made of polyethylene, polypropylene, polyvinyl chloride, or the like, which are formed by hollow molding or heat-bonding. Among them, the soft bag has the advantages of being lightweight and having a small volume at the time of disposal, and is not required to use a ventilating needle which may cause nosocomial infection during administration, and has become a mainstream of medical containers.

Conventionally, a film used in a soft bag is made of a polyolefin material such as polyethylene or polypropylene in order to reduce the elution at the time of steam sterilization under high air pressure and to maintain transparency and flexibility. However, polyolefin materials have a high degree of oxygen permeability. Therefore, in order to prevent deterioration of the chemical liquid from the outside, it has been proposed to coat the soft bag with an outer covering material having a high oxygen barrier property, such as Patent Document 1. The outer covering material may include a coating material other than a layer composed of a metal foil, an inorganic deposited film, or the like.

However, the amino acid infusion or the fat infusion or the like is dissolved, mixed, suspended, stirred, and transported by suction during the preparation and filling steps, and the air is mixed thereinto and remains as dissolved oxygen in the chemical solution. The dissolved oxygen concentration is known to be 3 to 50 ppm, and the oxidative degradation of the chemical solution itself is promoted. The reaction rate of oxidative degradation is accelerated in logarithmic scale with temperature. That is, oxidative degradation increases sharply when the steam sterilization step is performed under high pressure. In order to prevent the above-mentioned situation, the outer packaging of the infusion bag proposed by the patent documents 2, 3, etc. has been implemented, and the deoxidizer is contained or laminated, and the inside of the outer package of the infusion bag is filled with an inert gas, and the liquid medicine is used. A method in which an inert gas is substituted and simultaneously filled, and an antioxidant is added to the chemical solution. Inclusion or lamination of a deoxidizing agent, filling with an inert gas or the like contributes to suppression of oxidative degradation, but it is a concern that the barrier package is damaged or the needle is punctured. Further, in the lamination of the prior art, since the dry film method using an organic solvent as a medium is within the range of the dissolution test prescribed by the Japanese Pharmacopoeia, not only the amount of the eluted matter cannot be ignored, but also the foreign matter in the filming step is also feared. The exposed laminate interface. Further, the antioxidant added to the chemical solution may be vitamin C (ascorbic acid), vitamin E (tocopherol), BHT (dibutylhydroxytoluene), BHA (butylhydroxymethoxybenzene), sodium erythorbate or sodium sulfite. Sulfur dioxide, coffee bean extract (chlorogenic acid), green tea extract (catechin), rosemary extract, etc., are widely used as additives because of the excellent oxidation resistance of sulfite ionic substances. Because it is the cause of anaphylactic shock, it is not suitable for the human body.

From the above background, the invention proposed below provides an oxygen barrier property or an oxygen absorbing function to the container itself which is in direct contact with the medical drug solution.

Patent Document 4 proposes to use a die-casting co-extrusion method to form a film from the outer side of the layer of "polyamide or polyester or polyolefin layer", "bonding layer", "core layer of ethylene-vinyl alcohol copolymer" A five-layer structure such as "bonding layer" or "solution contact layer of polyolefin". The structure of this publication has an excellent oxygen barrier property but does not have an autologous oxygen absorption function. Further, since the film is formed by the inner surface being turned out during the die casting, the solution contact surface is exposed to the outside in the film forming step of the soft bag, and countermeasures for foreign matter to be mixed into the bag are necessary.

Patent Document 5 proposes to use a co-extrusion method to form a film from the outer side at least "an oxygen barrier layer composed of an ethylene-vinyl alcohol copolymer," an "oxygen-absorbing gas barrier layer a", and an "oxygen absorption". A multilayer structure of a gas barrier b layer" and a "heat sealable resin layer". This publication has excellent oxygen barrier properties and oxygen absorption properties in a normal temperature environment, but the outermost ethylene-vinyl alcohol copolymer lacks moisture resistance, and a medical container that requires hot water treatment such as steam sterilization under high pressure. It is not good to produce whitening.

Prior technical document Patent document

Patent Document 1: Special Publication No. 2005-280749

Patent Document 2: JP-A-2009-154924

Patent Document 3: JP-A-2008-37065

Patent Document 4: Special Open 2009-22753

Patent Document 5: JP-A-2007-283565

As described above, in the past, in order to prevent oxidative degradation of the chemical solution due to oxygen Packaging, there are problems as described below. Such problems include, for example, damage to the outer package or pinholes, dissolution of the solvent due to the use of an organic solvent, anaphylactic shock due to the antioxidant added to the chemical solution, oxidative degradation due to dissolved oxygen, and foreign matter incorporation. Whitening is caused by insufficient moisture resistance and high pressure steam sterilization.

In order to achieve the above object, the present invention employs the following means. that is,

(1) The present invention relates to a plastic film for a medical container having an oxygen absorbing function, which is obtained by condensation polymerization of an indoleamine having a carbon number of 11 or more, or an ω-amino acid having a carbon number of 11 or more. Polyamine or a first layer composed of a polyamidene obtained by co-condensation polymerization of a dicarboxylic acid having 10 or more carbon atoms and a diamine having 6 or more carbon atoms, adjacent to the first layer, and ethylene-vinyl alcohol a co-polymer as a main component, a second layer of a mixed composition having a polyene polymer having an unsaturated double bond and a transition metal salt as a subcomponent, adjacent to the second layer, and an α-olefin and an unsaturated carboxyl group a third layer of a copolymer of an anhydride of an acid or an unsaturated dicarboxylic acid as a main component, and at least four layers of a sealing layer containing a polyethylene as a main component, and is blown by a water-cooled type which is co-pressed. Membrane method is used for film formation.

(2) The present invention relates to a plastic film for a medical container having an oxygen absorbing function, which is obtained by condensation polymerization of an indoleamine having a carbon number of 11 or more or a ω-amino acid having a carbon number of 11 or more. Polyamide or a first layer composed of a polyamidene obtained by co-condensation polymerization of a dicarboxylic acid having 10 or more carbon atoms and a diamine having 6 or more carbon atoms, adjacent to the first layer, and an α-olefin and The copolymer of an unsaturated carboxylic acid or an anhydrous monomer of an unsaturated dicarboxylic acid is a second component of the main component, adjacent to the second layer, and has an ethylene-vinyl alcohol copolymer as a main component to have an unsaturated double The polyene polymer and the transition metal salt of the bond are the third layer of the mixed composition of the subcomponents, adjacent to the third layer, and the anhydrous monomer of the α-olefin and the unsaturated carboxylic acid or the unsaturated dicarboxylic acid. The fourth layer of the copolymer as a main component and at least five layers of a sealing layer mainly composed of polyethylene are formed by a water-cooling blown film method which is co-pressed.

(3) The plastic film for a medical container according to the above (1) or (2), wherein the ethylene-vinyl alcohol copolymer is a main component, and the polyene polymer having a unsaturated double bond and a transition metal salt are used. The layer of the mixed composition of the subcomponents can absorb 30 cc or more of oxygen per 1 g, and the thickness of the layer of the mixed composition is 5 to 35%.

(4) The plastic film for medical containers according to the above (1) to (3), wherein the melting temperature of the first layer is 175 ° C or higher, and the difference between the melting peak temperature of the sealing layer is 40 ° C the above.

(5) The plastic film according to (1) or (2) above, wherein the sealing layer is a mixture of 60 to 95% by mass of linear low-density polyethylene and 5 to 40% by mass of high-density polyethylene.

(6) The plastic film according to any one of the above items (1) to (3) wherein the sealing layer is a combination of an α-olefin and an unsaturated carboxylic acid or an unsaturated dicarboxylic acid. The polymer is composed mainly of the layer adjacent to the fourth layer and the layer formed of the high-density polyethylene adjacent to the layer.

(7) The present invention is an infusion bag, such as (1) to (6) The infusion bag formed of the plastic film of any one of the items, wherein the body is provided with an injection port.

According to the present invention, it is possible to provide a barrier to oxygen which is excellent in preventing intrusion of the outside while absorbing oxygen dissolved in the chemical solution, and has excellent safety and hygienic properties in accordance with the Japanese Pharmacopoeia, and is heat sealed at a high temperature for a short period of time. The film can be easily formed into a bag, and the possibility of mixing foreign matter from the outside of the film layer is extremely low, and a plastic film having heat resistance, transparency, flexibility, and impact strength comparable to 121 ° C high-pressure steam sterilization can be obtained. Further, the infusion bag manufactured from the plastic film of the present invention has the above-described features.

The invention is described in more detail below.

The layer structure of an example of the plastic film according to the first embodiment of the present invention is as shown in Fig. 1 . The film must have four layers composed of the first layer 1, the second layer 2, the third layer 3, and the sealing layer 4 from top to bottom.

The first layer 1 (hereinafter referred to as the outermost layer) is a polydecylamine obtained by ring-opening polymerization of an indoleamine having a carbon number of 11 or more or a ω-amino acid having a carbon number of 11 or more, or a carbon number of 10 or more. A layer composed of a polydecylamine obtained by co-condensation polymerization of a dicarboxylic acid and a diamine having 6 or more carbon atoms. The second layer 2 (hereinafter referred to as an oxygen absorbing layer) is adjacent to the first layer 1, and has an ethylene-vinyl alcohol copolymer as a main component, and a polyene polymer having an unsaturated double bond and a transition metal salt. A layer of a mixture of subcomponents. The third layer 3 (hereinafter referred to as an interlayer adhesion layer) is a layer mainly composed of a copolymer of an α-olefin and an anhydrous monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid, which is adjacent to the second layer 2 and mainly composed of a copolymer of an α-olefin and an unsaturated carboxylic acid. . seal Layer 4 is a layer mainly composed of polyethylene.

The outermost layer is a buffer layer which is damaged by external heating when the discharge of the chemical liquid called the injection port and the injection port part are carried out in the step of performing the heat-sealing process. The first layer 1 is composed of a polydecylamine obtained by ring-opening polymerization of an indoleamine having a carbon number of 11 or more or a ω-amino acid having a carbon number of 11 or more. Further, the first layer 1 is composed of a polydecylamine obtained by co-condensation polymerization of a dicarboxylic acid having 10 or more carbon atoms and a diamine having 6 or more carbon atoms.

The carbon number of the indoleamine which is subjected to ring-opening polymerization is 11 or more, and the upper limit of the carbon number is 12. When the carbon number of the mesaconamine monomer is less than 11, the de-cohesion reaction which is easy to produce polyamine is used at a high temperature, and the medical container not only fails to meet the specifications of the predetermined dissolution test, but also has a high hygroscopicity at a high temperature. It is easy to cause whitening when steam sterilization.

The mesalamine may, for example, be undecane decylamine or dodecyl decylamine. The ring-opening polymerization method is a well-known method for producing polyamine, and there are also commercially available products. Nylon 11 can be obtained by ring-opening polymerization of undecane indoleamine, and ring-opening polymerization of dodecyl decylamine can be carried out to obtain nylon 12.

When the ω-amino acid is subjected to condensation polymerization, the carbon number is 11 or more, and the upper limit of the carbon number is 12. When the carbon number is less than 11, the same problem as the polyamine which is obtained by ring-opening polymerization of indoleamine is the same. Examples of the ω-amino acid include ω-aminoundecanoic acid and ω-aminododecanoic acid. The method of condensation polymerization is a well-known method for producing polyamine, and there are also commercially available products.

The dicarboxylic acid in the case of co-condensation polymerization of a dicarboxylic acid and a diamine has a carbon number of 10 or more and an upper limit of carbon number of 12. Examples of the dicarboxylic acid include sebacic acid, dodecanedioic acid, and the like. The diamine has a carbon number of 6 or more. The diamine may, for example, be hexamethylenediamine or the like. Co-shrink The method of polymerization is a well-known method for producing polyamine, and there are also commercially available products. Nylon 610 can be obtained by co-condensation polymerization of sebacic acid with hexamethylenediamine, and nylon 612 can be obtained by co-condensation polymerization of dodecanedioic acid and hexamethylenediamine.

The polyamine obtained by any of the three methods may be used singly or in any ratio.

The melting peak temperature of the polyamine used is preferably 175 ° C or higher, more preferably 175 ° C to 245 ° C, and most preferably 175 ° C to 230 ° C. The measurement method of this melting peak was measured using a differential scanning calorimeter: DSC based on JIS-K7121.

The thickness of the first layer 1 is preferably 2 to 15% with respect to the total thickness, and more preferably 2 to 10%. 2~8% is the best. When the thickness of the first layer 1 is less than 2%, the cushioning fruit for damage due to heat transfer cannot be sufficiently exhibited at the time of sealing, and when the thickness of the first layer 1 exceeds 15%, the rigidity of the multilayer film is remarkably increased, and the damage is increased. And the softness of the medical container.

The second layer 2 type oxygen absorbing layer is a mixed composition containing an ethylene-vinyl alcohol copolymer as a main component and a polyene polymer having an unsaturated double bond and a transition metal salt as a subcomponent.

The ethylene-vinyl alcohol copolymer is mainly composed, and the ethylene content is preferably 25 to 45 mol%, more preferably 27 to 44 mol%.

The polyene polymer having an unsaturated double bond as an accessory component is a polymer having a hydrocarbon having 2 or more double bonds. The conjugated diene polymer is preferred, and examples thereof include polyisoprene or polyisoprene which are cis- or trans-1,4-isoprene polymers of a linear conjugated diene. a polybutadiene containing a cyclic polyisoprene and a polybutadiene of a 1,3-butadiene polymer of a linear conjugated diene obtained by a cyclic reaction A linear polymer such as polybutadiene containing a cyclized polybutadiene and a cyclic polymer obtained by a cyclic reaction. The content of the polyene polymer is preferably from 20 to 40% by mass, more preferably from 25 to 35% by mass.

The transition metal salt of the accessory component may, for example, be a salt of iron, nickel, copper, manganese, cobalt, rhodium, titanium, chromium, vanadium or ruthenium. The acid suitable for forming a salt is an organic acid, particularly preferably a monocarboxylic acid such as stearic acid, neodecanoic acid or the like. Preferred examples of the transition metal salt include cobalt stearate and cobalt neodecanoate. The content of the migration metal salt is preferably from 50 to 500 ppm, more preferably from 100 to 300 ppm.

The polyene polymer and the transition metal salt mixed with the ethylene-vinyl alcohol copolymer as a main component are oxidative cleavage reaction of the polyene polymer by using a migrating metal salt as a catalyst to form an alcohol. The aldehyde, ketone, and carboxylic acid simultaneously absorb oxygen. The composition of the mixture in the present invention is preferably a conjugated diene component containing 1 gram of oxygen which can absorb 30 cc or more. The thickness of the second layer 2 is preferably 5 to 35% of the total thickness of the plastic film, and more preferably 10 to 30%. When the thickness of the second layer 2 is less than 5% of the total thickness, the oxygen absorbing ability is insufficient. On the other hand, when the thickness of the second layer 2 exceeds 35%, it has a desired oxygen absorption capacity or more. Further, the physical strength of the film is impaired, and the manufacturing cost is unnecessarily increased.

For the mixed composition having an oxygen absorbing function, "PROACT" manufactured by Kuraray Co., Ltd., "QUINTIA" manufactured by Zeon Co., Ltd., and the like can be used as a commercial product.

A third layer 3, a second layer 2, and a sealing layer 4 to be described later, having a moisture-proof interlayer, a copolymerization of an α-olefin with an unsaturated monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid The main component.

The α-olefin system may, for example, be ethylene or propylene. A polyolefin which is ethylene or propylene alone or in a polymer, which can be obtained by using a catalyst unit obtained from a self-migrating metal compound and an organoaluminum compound, or by a monomer such as cerium oxide. It is obtained by separately polymerizing or copolymerizing a catalyst meter (Philipn catalyst) obtained by supporting a chromium compound (for example, chromium oxide) or an olefin using a radical initiator (for example, an organic peroxide).

Further, the anhydrous monohydrate system of the unsaturated carboxylic acid or the unsaturated dicarboxylic acid used in the present invention means a compound containing at least one double bond and having at least one carboxyl group or an anhydride thereof, and exemplified (Meth)acrylic acid, maleic acid, fumaric acid, maleic anhydride, fumaric anhydride, itaconic acid, pyrocitric acid, nadic acid, itaconic anhydride, nadic anhydride, pyroguanic anhydride, and the like.

The copolymer of the α-olefin used in the third layer 3 and the anhydrous monomer of the unsaturated carboxylic acid or the unsaturated dicarboxylic acid means a graft copolymer of the above-mentioned unsaturated monomer of the polyolefin. The graft copolymerization is carried out by adding a mixture of 0.01 to 20 parts by mass of an unsaturated monomer to 0.001 to 20 parts by mass of an organic peroxide to 100 parts by mass of the polyolefin, and supplying it to an extruder to carry out a melting reaction. Available later.

The organic peroxide used in the present invention may, for example, be a tertiary butyl peroxybenzoate or a 2,5-dimethyl-2,5-di(peroxytributyl)hexane or two. Tertiary butanol peroxide. Among these organic peroxides, an organic peroxide having a one-minute half-life of 100 to 280 ° C is preferred, and an organic peroxide of 120 to 230 ° C is suitable. These organic peroxides may be used singly or in combination of two or more.

When the mixing of the unsaturated carboxylic acid or the anhydrous monomer of the unsaturated dicarboxylic acid is less than 0.01 parts by mass with respect to 100 parts by mass of the polyolefin, the obtained copolymer and the ethylene-vinyl alcohol copolymer and the polymerization described later Indoleamine may be deficient in adhesion. On the other hand, when it exceeds 20 parts by mass, the graft reaction efficiency is lowered, and not only a large amount of unreacted or separately polymerized unsaturated compound remains in the graft reaction, but also the original physical properties of the polyolefin are impaired.

When the mixing of the organic peroxide is less than 0.001 part by mass with respect to 100 parts by mass of the polyolefin, the intended graft copolymer cannot be obtained. On the other hand, when it exceeds 20 parts by mass, the original physical properties of the polyolefin are impaired.

The above mixture is put into a press machine which is generally used, and melt-kneading is carried out inside, and a graft reaction is also carried out, whereby a graft modified product is obtained. The extruder used at this time may be either a beltless belt or a belt type, but from the viewpoint of removing unreacted or separately polymerized unsaturated materials and decomposition products of organic peroxides, the belt extruder is good. Further, the kneading temperature is 230 to 300 ° C, depending on the polyolefin to be used and the organic peroxide, but it is preferably 230 to 250 ° C. Further, the residence time of the mixture in the extruder is 60 seconds or longer, and particularly preferably 90 seconds or longer. When the mixing temperature was less than 230 ° C, the grafting reaction could not proceed smoothly. On the contrary, when it exceeds 300 ° C, a part of the polyolefin will start to deteriorate. Further, when the residence time of the mixture in the extruder was less than 60 seconds, the target graft reaction could not be performed.

At present, a copolymer of an α-olefin and an anhydrous monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid is commercially available, and such commercially available products can also be used.

As the third layer 3, the above-mentioned copolymer may be used singly, and a mixed composition of a copolymer and a polyolefin may also be used. In the case of the latter, the ratio η (polyolefin) / η (copolymer) of the melt viscosity of the copolymer at the same temperature to the melt viscosity of the polyolefin is preferably 2.0 or more. When it is less than 2.0, since the copolymer and the polyolefin have a tendency to be uniformly finely dispersed, the polar group present at the interface between the ethylene-vinyl alcohol copolymer and the polyamine described later is diluted, and the tendency of the adhesion is lowered. .

The third layer 3 is a layer mainly composed of a copolymer of the above α-olefin and an unsaturated monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid, and the total amount of the third layer 3 may be composed of the copolymer. Made into. On the other hand, other resins may also be contained. The subsequent strength is reduced at this time, but according to the experimental results of the patent applicant, the third layer 3 can also be formed with a mixture of 50% copolymer and 50% polyethylene.

The thickness of the third layer 3 is preferably 2 to 15% of the total thickness of the plastic film, and more preferably 2 to 10%. When the thickness of the third layer 3 is less than 2%, the ethylene-vinyl alcohol copolymer and the polyamine described later are insufficiently formed. When the thickness of the third layer 3 exceeds 15%, the physical strength of the film is impaired. At the same time, it is not good to make the manufacturing cost unnecessary.

In the present invention, the sealing layer 4 refers to a layer adjacent to the inner side of the third layer 3 mainly composed of polyethylene, and may be a single layer or a plurality of layers. Examples of the sealing layer 4 include low density polyethylene, high density polyethylene, linear low density polyethylene, and a mixed composition of the monomers. Among these polyethylenes, 60 to 95% by mass of linear low-density polyethylene having excellent transparency, flexibility, and impact resistance is complementary to a mixture of 5 to 40% by mass of high-density polyethylene having excellent heat resistance. The physical properties are better.

The linear low-density polyethylene in the present invention means a copolymer of one or more α-olefins selected from the group consisting of ethylene and an α-olefin having 3 to 20 carbon atoms. Among the α-olefins having 3 to 20 carbon atoms, α-olefins having 3 to 12 carbon atoms are preferred. Specific examples thereof include butene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and 1-undecene. Butylene, 1-butene, 1-hexene, 1-octene are preferred. The content of the copolymer in the α-olefin is generally from 1 to 30 mol%, preferably from 3 to 20 mol%. Further, the linear low-density ethylene may be a melt index measured according to JIS-K7112-D having a density of 0.900 to 0.940 g/cm ³ and based on JIS-K7210 at a temperature of 190 ° C and a load of 21.18 N ( MFR) is preferably a linear low density polyethylene of 0.1 to 20 g/10 minutes.

In the present invention, a high-density polyethylene having a density of 0.940 to 0.970 g/cm ³ and an MFR of 0.1 to 20 g/10 minutes is preferred. Density and MFR were measured under the same conditions as linear low density ethylene.

Further, in order to improve transparency and heat resistance, a crystal nucleating agent may be added to the polyethylene of the sealing layer 4. Suitable crystal nucleating agents include, for example, a calcium salt of cyclohexanedicarboxylate and a mixture of zinc stearate. The effective amount is such that the nucleating agent can be mixed in an amount of 2.5% by mass or less based on the total mass of the sealing layer. Sealing layer 4. The lower limit of the amount of the nucleating agent added is about 0.5% by mass.

The melting peak temperature of the sealing layer 4 is equal to or lower than the melting peak temperature of the first layer 1, and the difference between the melting peak temperature of the first layer 1 and the melting peak temperature of the sealing layer 4 is preferably 40 ° C or more, and 45 ° C or more. Better. When the temperature difference is less than 40 ° C, it is liable to be damaged by heat sealing. The upper limit of the temperature difference of the melting peak is not particularly limited, and is usually up to 100 °C. Melting point of the first layer 1 and the sealing layer 4 When the difference is too large, when the sealing layer 4 is also formed at a high temperature during the co-extrusion, the melt viscosity of the sealing layer 4 is remarkably lowered, and film formation cannot be performed stably.

The thickness of the sealing layer 4 is preferably 30 to 89% of the total thickness of the plastic film, 35 to 85%, and 35 to 80%. When the thickness of the sealing layer 4 is less than 30%, the physical strength of the film is impaired, and when it exceeds 89%, the thickness of the first to third layers described above is insufficient.

According to the fifteenth time, all the measured values of the test items specified in the first general test method of the plastic medicine container test method of the Japanese Pharmacopoeia are in accordance with the polyethylene or polypropylene water-based injection. The size of the container.

The layer structure of the modified example of the plastic film of the first embodiment is as shown in FIG. 2 . The film is composed of a first layer 1, a second layer 2, a third layer 3, and a sealing layer 41 for maintaining transparency and flexibility, and a layer 5 of a direct fusion sealing layer 42 adjacent to the sealing layer 41 from top to bottom. structure.

When the sealing layer is two layers, it is preferable that the sealing layer 41 is a main layer, and more specifically, the thickness ratio of the sealing layer 41 adjacent to the third layer to the direct molten sealing layer 42 is set to 50 to 97. : 50~3 is better, 70~95:30~5 is better.

Specifically, the sealing layer resin used is a sealing layer 41 adjacent to the third layer, which is a mixture of linear low-density polyethylene of 60 to 95% by mass and high-density polyethylene of 5 to 40% by mass, and the direct molten sealing layer 42 is A layer consisting only of high density polyethylene. By forming the layers, it is possible to surely prevent a portion of the adjacent film surface from sticking and agglomerating after autoclaving.

A layered structure of an example of a plastic film according to a second embodiment of the present invention As shown in Figure 3. The film has a five-layer structure composed of the first layer 1, the second layer 31, the third layer 2, the fourth layer 32, and the sealing layer 4 from top to bottom. In the second embodiment of the plastic film of the present invention, the first layer 1 (outermost layer) is obtained by condensation polymerization of an indole amine having a carbon number of 11 or more or a ω-amino acid having a carbon number of 11 or more. A layer composed of polyamine which is obtained by co-condensation polymerization of a dicarboxylic acid having 10 or more carbon atoms and a diamine having 6 or more carbon atoms. The second layer 31 (the first interlayer adhesive layer) is a layer mainly composed of a copolymer of an α-olefin and an unsaturated monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid, which is adjacent to the first layer. The third layer 2 (oxygen absorbing layer) is adjacent to the second layer, and has an ethylene-vinyl alcohol copolymer as a main component, and a polyene polymer having an unsaturated double bond and a transition metal salt as a subcomponent. Mix the layers of the composition. The fourth layer 32 (the second interlayer adhesive layer) is a layer mainly composed of a copolymer of an α-olefin and an anhydrous monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid, which is adjacent to the third layer. The sealing layer 4 is a layer mainly composed of polyethylene.

The innermost layer, the outermost layer, the oxygen absorbing layer, the first and second interlayers, and the sealing layer (excluding the layer thickness) of the layers are the outermost layer, the oxygen absorbing layer, and the interlayer between the layers of the first embodiment. And the sealing layer is the same. The layer thickness of the sealing layer is preferably from 30 to 89% of the total layer, and more preferably from 35 to 85%.

In other words, the plastic film of the first embodiment differs from the plastic film of the second embodiment in that an interlayer sealing layer having moisture resistance is provided between the outermost layer and the oxygen absorbing layer. By arranging the adhesive layer, it is possible to suppress the whitening of the oxygen absorbing layer due to the high pressure steam sterilization step after moisture absorption.

The total thickness of the film of the present invention is not particularly limited, but after considering transparency, flexibility, impact resistance, water vapor permeability, etc., in the first embodiment Both the formula and the second embodiment are preferably in the range of 50 to 1000 μm, more preferably 100 to 350 μm, and particularly preferably 150 to 250 μm.

The layer structure of another example of the plastic film of the second embodiment is shown in Fig. 4 . The film includes a first layer 1 (outermost layer), a second layer (first layer interlayer) 31, a third layer (oxygen absorbing layer) 2, and a fourth layer (second interlayer layer) 32 from top to bottom. Six layers of the fifth layer (sealing layer for maintaining transparency and flexibility) 41 and the sixth layer (direct sealing layer) 42 are formed.

An example of the infusion bag of the present invention made using the plastic film of the present invention is shown in Fig. 5.

The infusion bag is a first end of an infusion bag composed of a tubular plastic film 10, and is provided with an injection port 11 and then heat-sealed, and the first end heat sealing portion 12 is used as a bottom portion, and then filled from the infusion storage portion 13 After infusion, it is heat sealed at the second end. In the center of the second end heat sealing portion 14, a hole is formed through the hole to form a hanging hole 15, and a rectangular unsealed portion 16 is provided on both sides thereof. The front end of the injection port 11 is provided with a rubber crucible into which an injection needle can be inserted. In addition, the injection port can also be tubular.

In the plastic film of the present invention, at least four or more films are formed into a multilayer film in one step by a co-extrusion method. The co-extrusion method may be a film formation of a sheet formed by multilayer T molding, or a film formation by a multi-layer blown film, but when a medical container bag is produced, in order to store the liquid medicine The inner surface of the film is not easily exposed to the outside but is preferably in the form of a cylinder. Further, in order to exhibit high transparency, a water-cooled co-extrusion blown film method in which a quenching and solidification is applied from a molten state is preferred.

[Examples]

The invention will be more specifically described by way of examples.

In Examples 1 to 4 and Comparative Examples 1 to 3, the first layer, the second layer, the third layer, the fourth layer, and the sealing layer were formed into a plastic film by using a different resin. Thereafter, the specific film was subjected to autoclaving, and the film after the autoclaving and the film which was not autoclaved were subjected to dissolved oxygen concentration, atomization, appearance and agglomeration after standing for 14 days. Evaluation.

‧ Resin used in each layer:

In the examples 1 to 4 and the comparative examples 1 to 3, the following resins were used for the first layer, the second layer, the third layer, the fourth layer, and the sealing layer.

PA11: Nylon 11, manufactured by Arkema, RILSAN "BESV 0 AF DA" density = 1.02 g/cm ³ , melting peak temperature = 184 ° C

AD: Butane dianhydride grafted polypropylene, ZELAS "MC721AP" density by Mitsubishi Chemical = 0.89 g / cm ³ , MFR = 3.5 g / 10 min, melting peak temperature = 155 ° C

LLD: Linear low density polyethylene, manufactured by Primepolymer, Evolue "SP0511" density = 0.993 g/cm ³ , MFR = 1.2 g/10 min, melting peak temperature = 110.1 ° C

HD: high density polyethylene, made of Japanese polyethylene, NOVATEC density = 0.955 g/cm ³ , MFR = 3.5 g/10 min, melting peak temperature = 132.4 ° C

ACT: a polyene polymer having an unsaturated double bond mainly composed of an ethylene-vinyl alcohol copolymer, manufactured by Kuraray, PROACT "XEP1190B" density = 1.19 g/cm ³ , MFR = 4.0 g/10 min, melting peak Temperature = 191 ° C

EVOH: ethylene-vinyl alcohol copolymer, manufactured by Kuraray, EVAL "L171B" density = 1.20 g/cm ³ , MFR = 4.0 g/10 min, melting peak temperature = 191 ° C

A mixture of 80% by mass of LLD and 20% by mass of HD was used in the sealing layers of Examples 1 and 2 and Comparative Examples 1 to 3, and in the first layer of Comparative Example 3. The mixture had a melting peak temperature = 125 °C.

The sealing layer of Example 4 is a layer of 120 μm which is composed of LLD (80%) + HD (20%) adjacent to the fourth layer, and a direct molten sealing layer composed of 100% HD adjacent to the fourth layer. This layer consists of 10 μm.

‧ Film forming method for plastic film layer:

The film formation of the plastic film layer was carried out under the following conditions using five types of five or six types of six-layer water-cooling film forming machine.

The first layer: a screw extruder with an outer diameter of 40 mm and a compression ratio of 2.7 (extrusion temperature of 200 ° C)

The second layer: a screw extruder with an outer diameter of 40 mm and a compression ratio of 2.7 (extrusion temperature of 200 ° C)

The third layer: a screw extruder with an outer diameter of 40 mm and a compression ratio of 2.7 (extrusion temperature of 200 ° C)

The fourth layer: a screw extruder with an outer diameter of 40 mm and a compression ratio of 2.7 (extrusion temperature of 200 ° C)

In the extruder for the fourth layer, in Example 2 and Comparative Example 2, only the temperature rise was performed.

Sealing layer: screw extruder with outer diameter of 65 mm and compression ratio of 1.4 (extrusion temperature 210 ° C)

Mold: outer diameter 200 mm, spout interval 3 mm, temperature 210 °C

Blowing ratio: 0.6

Film forming speed: 13 m/min

Water cooling: the outer diameter of the spout is 120 mm, and the water temperature is 11.5 °C.

The obtained film was prepared into a bag, and the dissolved oxygen concentration and atomization were measured, and the appearance and agglomeration were evaluated.

‧ Evaluation of sample preparation ‧ Determination of dissolved oxygen concentration:

Two sheets of the above-mentioned film which were formed into a cylindrical film were heat-sealed at a temperature of 210 ° C and a pressure of 0.2 MPa for 0.5 second to prepare a three-side heat-sealed bag having an inner diameter of 100 × 100 mm. In order to measure the dissolved oxygen concentration, the detection wafer for measuring the dissolved oxygen concentration is fixed to the inner surface of the three-side heat-sealed bag by a dedicated adhesive. The distilled water having a dissolved oxygen concentration of 7.0 to 7.5 ppm was transferred to a glass vessel with a vacuum pump and attached thereto in an undisturbed state in a constant temperature chamber at 23 °C. The sealed glass container was placed in an ultrasonic cleaning tank for 10 minutes, and ultrasonic waves were applied while degassing with a vacuum pump to prepare distilled water having a dissolved oxygen concentration of 4.8 to 6.3 ppm. 100 ml of the prepared distilled water was transferred to the aforementioned three-side heat-sealed bag in an undisturbed state, and the remaining side was quickly sealed with a heat seal. The sealed Examples 1, 3 and 4 and Comparative Examples 1 and 3 were autoclaved at 121 ° C for 25 minutes. Thereafter, all the samples were transferred to a constant temperature and humidity chamber at 40 ° C and 70% RH, and allowed to stand for 14 days. After 14 days, the stationary sample was taken out and moved to a constant temperature room at 23 ° C to cool it to 23 ° C.

Through the above treatment, the dissolved oxygen concentration in the bag was measured from the test wafer of the sample by a non-destructive oxygen concentration meter (Sanyo Trading Co., Ltd., Fibox-3 type).

‧ Evaluation of atomization:

In the first embodiment, the third embodiment, the fourth embodiment, the comparative example 1 and the comparative example 3, two sheets of the film formed by tubular molding were taken, and heat-sealed at a temperature of 210 ° C and a pressure of 0.2 MPa for 0.5 second. It is a three-side heat-sealed bag with a size of 100×100mm. The bag was filled with 100 ml of distilled water, and the remaining side was heat sealed. Next, autoclaving was carried out at 121 ° C for 25 minutes with a portion of the inner surface of the bag being tightly adhered. Thereafter, the distilled water was quickly opened and the test film of each of the examples and the comparative examples was subjected to a normal adjustment for 14 days under the environment of 23 ° C and 50 RH % temperature and humidity. The sample film was operated in accordance with JIS-K6714, and the degree of atomization was measured.

The film formed into a tubular film in Example 2 and Comparative Example 2 was placed in a 23 ° C, 50 RH % temperature and humidity environment for 14 days of normal adjustment. The sample film was operated in accordance with JIS-K6714, and the degree of atomization was measured.

‧ Evaluation of the production of the specimen ‧ Appearance and agglomeration evaluation:

The evaluation system takes two sheets of the above-mentioned film which are formed into a cylindrical film, so that the sealing layers are overlapped, and the heat sealing is performed for 0.5 second at a temperature of 210 ° C and a pressure of 0.2 MPa, and the inner layer is made of 100×100 mm. Heat sealed bag on the side. The bag was filled with 50 ml of distilled water to seal the remaining side with a heat seal. The inside of the bag was loaded in a tightly adhered manner, and autoclaved at 121 ° C for 25 minutes. The appearance of the bag was observed after autoclaving, and the presence or absence of wrinkles was visually evaluated.

The evaluation of the agglomeration was carried out after the autoclave was sterilized. It was found that the inner surface of the bag could be completely separated, but when some parts were still tightly adhered, it was recorded as "caking" and no part was found to be completely adhered. It is "no agglomeration".

The results obtained are shown in Table 1.

In the sample film of Table 1, in Examples 1, 3, and 4 and Comparative Examples 1 and 3, AD was provided in the interlayer between the layers on both sides of the oxygen absorbing layer. In Example 2 and Comparative Example 2, AD was provided only on one side, and the oxygen absorbing layer was adjacent to the outermost layer (first layer).

According to the dissolved oxygen concentration, in the oxygen absorbing layers, the dissolved oxygen was not detected in Examples 1, 3, and 4 using ACT, but Comparative Examples 1 to 3 in which the EVOH was used in place of the oxygen absorbing layer showed a high detection value. From this, it is understood that in order for the oxygen absorbing layer to function, it is necessary to use not only an ethylene-vinyl alcohol copolymer as a main component but also a polyene polymer having an unsaturated double bond.

Comparing Example 2 with Comparative Example 2, it was also found that the comparative oxygen concentration of EVOH was used instead of the oxygen absorbing layer, and the dissolved oxygen concentration was measured.

Focusing on the result of agglomeration of the sealing layer, in addition to Example 4 in which the sealing layer was composed of two layers, when the bag was opened after autoclaving, no significant hindrance was observed during use, but at least a part was shown to be tight. Adhesive. Therefore, from the results of Example 4, it was confirmed that the sealing layer did not agglomerate by containing a direct-dissolving sealing layer composed only of high-density polyethylene. However, when the sealing layer was composed only of linear low-density polyethylene, it was found from Example 3 that wrinkles were generated, and the atomization was worse than the other examples.

In the first layer of Comparative Example 3, a film of the same resin as the sealing layer was used. The evaluation results of agglomeration and wrinkles were the same as those of Example 1 and Comparative Example 1, but the atomization condition was poor, and the result of the dissolved oxygen concentration was further inferior.

When focusing on the difference between the melting peak temperature of the first layer and the melting peak temperature of the sealing layer, for example, in Example 4, the first layer (184 ° C: PA11)-sealing layer (132 ° C: HD 100%) has a difference of 52 ° C. . However, in Comparative Example 3, since the first layer was made of the same resin as the sealing layer, the difference in melting peak temperatures was 0 °C.

From the above results, it was found that the outermost layer of the nylon 11 having a carbon number of 11 or more, the ACT containing the polyene polymer having an unsaturated double bond as the oxygen absorbing layer, and the AD as the interlayer of the interlayer on the ACT side. That is, the first interlayer adhesive layer and the second interlayer adhesive layer are provided, and the sealing layer is a sealing layer for maintaining general transparency and flexibility, a direct melt sealing layer, and a layer containing both layers, although It has a slight atomization, but it has excellent oxygen absorption function, and the sealing layer is not wrinkled and agglomerated, which is a suitable film.

[Industrial availability]

The plastic film of the invention does not require an outer covering material, and does not use an organic solvent-based adhesive, can effectively absorb dissolved oxygen in the chemical liquid, and can be widely used in infusion and enteral nutrition because it does not cause whitening problem of high-pressure steam sterilization. Medical containers such as agents.

1. . . Outermost layer

2. . . Oxygen absorbing layer

3, 31, 32. . . Interlayer

4. . . Sealing layer

10. . . Plastic film

11. . . Note entry

12. . . First end heat seal

13. . . Infusion storage unit

14. . . Second end heat seal

15. . . Suspension hole

16. . . Unsealed part

41. . . Sealing layer that maintains transparency and softness

42. . . Direct melt seal

Fig. 1 is a partial cross-sectional view showing an example of a plastic film of the present invention.

Fig. 2 is a partial cross-sectional view showing a modification of the plastic film of the present invention.

Fig. 3 is a partial cross-sectional view showing a modification of the plastic film of the present invention.

Fig. 4 is a partial cross-sectional view showing a modification of the plastic film of the present invention.

Fig. 5 is a plan view showing an example of an infusion bag made of the plastic film of the present invention.

1. . . Outermost layer

2. . . Oxygen absorbing layer

3. . . Interlayer

4. . . Sealing layer

Claims (7)

A plastic film for a medical container having an oxygen absorbing function, which is obtained by condensation polymerization of an indoleamine having a carbon number of 11 or more or a ω-amino acid having a carbon number of 11 or more, or a first layer composed of a polydecylamine obtained by co-condensation polymerization of a dicarboxylic acid having 10 or more carbon atoms and a diamine having 6 or more carbon atoms, adjacent to the first layer, and comprising an ethylene-vinyl alcohol copolymer as a main component a second layer of a mixed composition having a polyene polymer having an unsaturated double bond and a transition metal salt as a subcomponent, adjacent to the second layer, and an α-olefin and an unsaturated carboxylic acid or an unsaturated dicarboxylic acid A film in which a copolymer of an acid anhydride monomer is a third component of a main component and at least four layers of a sealing layer containing polyethylene as a main component, and is formed by a water-cooling blown film method which is co-extrusion The melting peak temperature of the first layer is 175 ° C or higher, and the difference between the melting peak temperature of the sealing layer is 40 ° C or higher. A plastic film for a medical container having an oxygen absorbing function, which is obtained by condensation polymerization of an indoleamine having a carbon number of 11 or more or a ω-amino acid having a carbon number of 11 or more, or a first layer composed of a polydecylamine obtained by co-condensation polymerization of a dicarboxylic acid having 10 or more carbon atoms and a diamine having 6 or more carbon atoms, adjacent to the first layer, and an α-olefin and an unsaturated carboxylic acid or not a copolymer of a saturated dicarboxylic acid anhydrous monomer as a second component of a main component, Adjacent to the second layer, the third layer and the third layer of the mixed composition of the ethylene-vinyl alcohol copolymer as a main component and the polyene polymer having an unsaturated double bond and the transition metal salt as a subcomponent a fourth layer comprising a copolymer of an α-olefin and an unsaturated monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid as a main component, and at least 5 layers of a sealing layer containing a polyethylene as a main component The film formation is carried out by a water-cooling blown film method in which the first layer has a melting peak temperature of 175 ° C or higher, and the difference between the melting peak temperature of the sealing layer and the sealing layer is 40 ° C or higher. A plastic film for medical containers according to claim 1 or 2, wherein an ethylene-vinyl alcohol copolymer is used as a main component, and a polyene polymer having an unsaturated double bond and a transition metal salt are used as a subcomponent The layer of the mixed composition can absorb 30 cc or more of oxygen per 1 g, and the thickness of the layer of the mixed composition is 5 to 35%. The plastic film according to claim 1 or 2, wherein the sealing layer is a mixture of 60 to 95% by mass of linear low density polyethylene and 5 to 40% by mass of high density polyethylene. The plastic film according to claim 1, wherein the sealing layer is the third component which is mainly composed of a copolymer of an α-olefin and an anhydrous monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid. The layer adjacent to the layer and the layer formed of the high-density polyethylene adjacent to the layer are composed of two layers. An infusion bag, which is an infusion bag composed of a plastic film according to claim 1 or 2, and an injection port is provided on the body. Such as the plastic film of claim 2, wherein the seal The layer is a layer adjacent to the fourth layer mainly composed of a copolymer of an α-olefin and an anhydrous monomer of an unsaturated carboxylic acid or an unsaturated dicarboxylic acid, and a high-density polyethylene adjacent to the layer The formed layer is composed of two layers.